N-(indazolyl-n1-methyl)dialkanolamines

ABSTRACT

COMPOUNDS THAT HAVE THE STRUCTURAL FORMULA WHREIN X REPRESENTS HALOGEN, NITRO, AMINO, ACETAMINO, OR (HALOBENZYLIDENE) AMINO; Y REPRESEENTS HYDROGEN OR HALOGEN; R AND R&#39;&#39; EACH REPRESENTS AN ALKYLENE GROUP HAVING 1 TO 8 CARBON ATOMS; AND N REPESENNTS A NUMBER IN THE RANGE OF 0 TO 3 ARE USED TO CONTROL THE GROWTH OF FUNGI AND BACTERIA. ILLUSTRATIVE OF THESE COMPOUNDS IS N-(3-CHLOROINDAZOLYL-N1-METHYL)DIETHANOLAMINE.   1-(HO-R-N(-R&#39;&#39;-OH)-CH2-),3-Y,(X)N-1H-INDAZOLE

United States Patent ()1 ice Patented Aug. 6, 1974 3,828,067 N-(lNDAZOLYL-N METHYL) DIALKANOLAMINES Pasquale P. Minieri, Woodside, N.Y., assignor to Tenneco Chemicals, Inc.

No Drawing. Filed Nov. 20, 1972, Ser. No. 308,156

Int. Cl. C07d 49/18 U.S. Cl. 260-310 C a 3 Claims ABSTRACT OF THE DISCLOSURE Compounds that have the structural formula R andR' each represents an al'kylene group having 2 0r 3 canbon atoms. Among the preferred compounds are The novel compounds may be prepared by any suita- C-Y x his and convenient procedure. For example; they may be prepared by heating an N -hydroxymethylindazole with R-OH the appropriate alkanolamine. The reaction is generally carried out in a solvent, such as toluene, acetone, or RLOH tetrahydrofuran, at the reflux temperature of the reaction wherein X represents halogen, nitro, amino, acetamino, or (halobenzylidenwamino; Y represents hydrogen or halogen; R and IR each represents an alkylene group having 1 to 8 carbon atoms; and n represents a number in the range of 0 to 3 are used to control the growth of fungi and bacteria. Illustrative of these compounds is N-(3-chloroindazolyl-N -rnethyl)diethanolarnlne.

This invention relates to N=(lndazoiyl N =rnethyl) dialkanolarnines and to the use of these compounds in the control of the growth of bacteria, fungi, and other microorganisms.

In accordance with this invention, it has been found that certain N (indazoiyl N rnethybdialltanolarnines have unusual and valuable activity as bioeides. These cone pounds may be represented by the structural formula N- ind azolyl-N -methyl diethanolamine,

" N-(3-chloroindazolyl-N -methyl)dipropanolamine,

N-(3-bromo-5,6-dinitroindazolyl-'N -methyl)dioctanol N- (3 ,5 -difiuoroindazolyl- N -methyl dibutanolamine, N-( 3,6-diodoindazolyl-N -methyl)dihexanolamine,

(G-acetaminoindazolyl-N -methy1 )dipropanolamine, N- (4,7-diaminoindazolyl-N -rnethyl dimethanolamine, N- 6- (chlorobenzylidene) aminoind azolyl-N -methy1] ethanolpropanolamine, N- 4,5 ,7 -trichloroindazolyl-N -rnethyl -diethanolamine, N- 5,7-dichloroindazolyl-N -methyl diethanolamine,

{- 3-chloro-6- (p-bromobenzylidene) aminoindazolyl-N methyl] pro panolbutanolamine, N-(3,4,5,7-tetrabromoindazolyl-N -methyl)methanolpropanolamine,

and the like.

Particularly eflective as biocides are the compounds having the aforementioned structure in which X represents chlorine or nitro, Y represents chlorine or hydrogen, and

mixture.

The N-(indazolyhN -methybdialkanolamines can be used to inhibit or prevent the growth of a wide variety of fungi and bacteria.

In a preferred embodiment of the invention, the novel amines are used toyhnpart fungal and bacterial resistance to surface-coating composition including both organic sol vent based and water based coating systems. They are particularly valuable as blocides in coatings that contain as their resinous binder either an oleorcsinous material or a waterdnsoluble synthetic linear addition polymer.

Among the suriace=eoating compositions in which the compounds of this invention can be used as the biocide are organic solvent based systems that contain such oleo= resinous binders as drying oils, such as linseed oil, tung oil, soybean oil, dehydrated castor oil, saiiiower oil, or fish oil, bodied drying oils; blends of drying oils or bodied drying oils with a resin component such as lirncd rosin, an ester gum, or phenolic resin; oleoresinous varnishes formed by heating one of the aforementioned resins with one or more drying oils or bodied drying oils; alhyd resins, which are resinous products resulting irons. the reaction of a poiyhydrie alcohol, such as pentaerythrltol of glyc erol, with a diearboxylic acid, such as phthalie anhydride, and fatty acids; and mixtures thereof.

The novel amines can also be used as the biocide in aqueous dispersions that contain about 10 percent to 60 percent by weight of a water-insoluble resinous hinder that is an oleoresinous binder as hereinbefore defined, a syn thetic linear addition binder, or a mixture of an oleoresin ous binder and a synthetic linear addition binder. The aqueous dispersions of synthetic linear addition polymers are ordinarily prepared by the emulsion polymerization of ethylenically-unsaturated compounds, especially those of monoethylenicaliy-unsaturated character, although butadiene, chlorobuta'diene, and isoprene may be used to some extent. Illustrative of the synthetic linear addition polymers that can be used as the resinous binder in the aqueous dispersions are polyvinyl acetate; polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate with acrylonitrile; copolymers of vinyl chloride with vinyl acetate, acrylonitrile or vinylidene chloride; "polyethylene; polyisobutylene; polystyrene; copolymers of styrene with maleic anhydride or butadiene; copolymers of acrylonitrile with butadiene; copolymers of methacrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene; copolymers of acrylic acid esters of alcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride, acrylonitrile, or styrene;

and mixtures thereof.

Only a small amount of the N-( indazo1y1-N -methyl)dialkanolamine need be present in the surface-coating com positions. As little as 0.10 percent of one or more of these compounds, based on the weight of the composition, will bring about an appreciable improvement in the resistance of the compositions to attack by fungi and bacteria. Three percent or more can be used, but these larger amounts generally do not provide further improvement in the prop- C. An exterior house paint was prepared by mixing together the following materials:

erties of the surface-coating compositions and for this Basic lead carbonate reason are not ordinarily used. In most cases about 1 perr 2 fth 1 d b d th J Zlnc oxide 232 celilt to P 9 a compoun ase on 6 Titanium dioxide (rutfle) m 4 weight of the composition, is used.

Th 'n to 's furtheillu trated b th followin Talc w 260 g 1 1 S Y e g Linseed oil 242 Bodied linseed oil 114 EXAMPLE 1 l0 Mineral spirits 114 A mixture of 18.3 grams (0.1 mole) of N -hydroxy Antlskmnmg agent (Exkm 2 methyl 3 chloroindazole, 10.5 grams (0.1 mole) of Manganese naphthenate diethanolamine, and 150 ml. of toluene was heated at its Lead naphthenate reflux temperature until mole) of Water had D. To samples of these paints was added either 2 perbeef} F i- WaS heatfid at Y refiuX temperature an cent by weight of one of the compounds of this invention additional hour, cooled in an ice bath, and then filtered. or 2 percent by weight f a comparative biocideg The product was washed with toluene and dried at 40 C. EXA PL 4 under reduced pressure. There was obtained 26.1 grams M E (97% yield) of N-(3-chloroindazolyl-N -methyl)dieth- The acrylic paint, the polyvinyl acetate paint, and the anolarnine, which was a white solid that melted at 102.5 oil based paint whose preparation is described in Exam- 106.5 C. and that contained 12.3% C1 (calculated, 13.1% ple 3 were evaluated by means of an agar difiusion assay. Cl). In this test agar is inoculated with the test organism, the EXAMPLE 2 treated paint is placed in a well out from the agar, and f Q A mlxmre of 2L7 grams (0.1 mole) of N1 hy dmmh 5 a ter incubation at 2 8 C and 85 95% relative humid ty,

. the activity of the btocide is measured by zones of inhibimethyl-5,7-d1chlor01ndazo1e, 10.5 grams (0.1 mole) of tron. The biocidal compounds tested and the results obdiethanolamlne, and 150 ml. of toluene was heated at its mined am givfin in tha following table In this table reflux temperature until 1.8 ml. (0.1 mole) of water had Y been evolved. It was heated at its reflux temperature for an Z0: Zone of inhibition in mm. additional fifteen minutes after which 75 ml. of solvent 01 No g owthmo zone ofinhl tuon was distilled off under vacuum at 70 C. and the con- Tr: Trace of zone of inhibition centrate was cooled. The separated solids were filtered Not tested off, washed with cold toluene and the combined filtrate Bacteria and wash was stripped to dryness under vacuum to isolate ABacillus subtill's the product. There was obtained 21.4 grams (70.5% yield) .B-Aerobaeter flerogenes of N (5,7 dichloroindazolyl N methyUdiethanoh C-Pseudomorzas aeruginose amine. which was a yellow semi-solid and that contained Fungi,

24.1% Cl (calculated 23.4% Cl). g-PullulZria pullulans --Fenici .ium cruszosum EXAMPLE 3 d0 F ASPfl'gillllS nige r A. A. polyvinyl acetate emulsion paint was prepared by The compounds tested and the results obtained are e mixing together the following materials: forth in the following table.

TABLE nieetdal aetivlt mat /mt. t fi g .BlOUltiD Point 1311 A V V B V N i i E" V F Product of Examplel Acrylic 0.0 Tr 0 zo-s ZO-l zo-i 2 .1

PVA .3 ZO-fi 70-2 204 ZO-l 20-3 Tr 011 zo-1 zo-r Tr Product of Example 2 Tr ZO-l 0 Q T 'Ir TL 204. ZO-Z 'Ir W Tr ZO-1 Tr Bis( henylmereury)dodecenylsuecinato (Super Ad-it) ZO-t) Z0-5 ZO-Ei 210-8 ZO-B ZO-9 PV 2040 20s ZO-5 zo-10 ZO-fl ZO-17 20-7 7.0-4 Z0-10 Parts by Weight Water 280 Potassium pyrophosphate 3 Calcium metasilicate 135 Titanium dioxide (rutile) 220 2% Aqueous solution of methylcellulose 200 Diethyl ether of diethylene glycol 37 Aqueous dispersion of polyvinyl acetate 350 B. An acrylic paint was prepared by mixing together the following materials:

Each of the other N-(indazolyl-N -methyl)dialkanolamines disclosed herein can be used in a similar way to protect surface-coating compositions from deterioration resulting from attack by fungi and bacteria.

What is claimed is:

1. A compound having the structural formula wherein X represents halo; Y represents halo or hydrogen; R and R each represents alkylene of 1 to 8 carbon atoms; when Y is halo, n represents a number in the range of 0 to 3; and when Y is hydrogen, :1 represents a number in the range of 1 to 3.

5 6 2. N-(3-Chloroindazolyl-N -methyl)diethanolamine. Zhao et al.: Zhur. Obshchei Khim., Vol. 29, pp. 1012- 3. N (5,7 Dichloroindazolyl-N -methyl)diethanol- 20 (1959). amine.

References Cited NATALIE TROUSOF, Primary Exammer Pozharskii et al.: J. Gen. Chem. USSR, Vol. 34, pp. 5 US. Cl. X.R. 3409-11 0964)- 106-15 R, 15 AF, 18; 260-29.6 MN, 89.1; 424-273 Zhao et al.: Chem. Abst., Vol. 54, column 1500 (1960). 

